Oxetane

Oxetane

Oxetane

Chemical compound

Oxetane, or 1,3-propylene oxide, is a heterocyclic organic compound with the molecular formula C
3H
6O, having a four-membered ring with three carbon atoms and one oxygen atom.

Quick Facts Names, Identifiers ...

The term "an oxetane" or "oxetanes" refer to any organic compound containing the oxetane ring.

Production

A typical well-known method of preparation is the reaction of potassium hydroxide with 3-chloropropyl acetate at 150 °C:[2]

Yield of oxetane made this way is c. 40%, as the synthesis can lead to a variety of by-products including water, potassium chloride, and potassium acetate.

Another possible reaction to form an oxetane ring is the Paternò–Büchi reaction. The oxetane ring can also be formed through diol cyclization[3] as well as through decarboxylation of a six-membered cyclic carbonate.[citation needed]

Derivatives

More than a hundred different oxetanes have been synthesized.[4] Functional groups can be added into any desired position in the oxetane ring, including fully fluorinated (perfluorinated) and fully deuterated analogues. Major examples are:

More information Name, Structure ...

Taxol

Paclitaxel with oxetane ring at right.

Paclitaxel (Taxol) is an example of a natural product containing an oxetane ring. Taxol has become a major point of interest among researchers due to its unusual structure and success in the involvement of cancer treatment.[9] The attached oxetane ring is an important feature that is used for the binding of microtubules in structure activity; however little is known about how the reaction is catalyzed in nature, which creates a challenge for scientists trying to synthesize the product.[9]

Disparlure

Oxetane is used in one of the syntheses of Disparlure (Gypsy moth sexual pheromone).[10]

Reactions

Oxetanes are less reactive than epoxides, and generally unreactive in basic conditions,[11] although Grignard reagents at elevated temperatures[12] and complex hydrides will cleave them.[13] However, the ring strain does make them much more reactive than larger rings,[14] and oxetanes decompose in the presence of even mildly acidic nucleophiles.[15] In non-nucleophilic acids, they mainly isomerize to allyl alcohols.[16]

Noble metals tend to catalyze isomerization to a carbonyl.[17]

In industry, the parent compound, oxetane polymerizes to polyoxetane in the presence of a dry acid catalyst,[18] although the compound was described in 1967 as "rarely polymerized commercially".[19]

See also

References

  1. [1]
    Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. p. 147. doi:10.1039/9781849733069-FP001 (inactive 2024-04-15). ISBN 978-0-85404-182-4.{{cite book}}: CS1 maint: DOI inactive as of April 2024 (link)
  2. [2]
    C. R. Noller (1955). "Trimethylene Oxide". Organic Syntheses. 29: 92; Collected Volumes, vol. 3, p. 835.
  3. [3]
    Patai 1967, pp. 411–413.
  4. [4]
    Goethals, Lucien; Sioen, Philip (2000). "Dialogos. Lucien Goethals in gesprek met Philip Sioen". Revue belge de Musicologie / Belgisch Tijdschrift voor Muziekwetenschap. 54: 49–71. doi:10.2307/3686877. ISSN 0771-6788. JSTOR 3686877.
  5. [5]
    "78-71-7 CAS MSDS (3,3-BIS(CHLOROMETHYL)OXETANE) Melting Point Boiling Point Density CAS Chemical Properties". www.chemicalbook.com. Retrieved 2022-12-28.
  6. [6]
    Akhtar, Tauseef; Berger, Ronald; Marine, Joseph E; Daimee, Usama A; Calkins, Hugh; Spragg, David (2020-08-13). "Cryoballoon Ablation of Atrial Fibrillation in Octogenarians". Arrhythmia & Electrophysiology Review. 9 (2): 104–107. doi:10.15420/aer.2020.18. ISSN 2050-3377. PMC 7491081. PMID 32983532.
  7. [7]
    Baum, Kurt; Berkowitz, Phillip T.; Grakauskas, Vytautas; Archibald, Thomas G. (September 1983). "Synthesis of electron-deficient oxetanes. 3-Azidooxetane, 3-nitrooxetane, and 3,3-dinitrooxetane". The Journal of Organic Chemistry. 48 (18): 2953–2956. doi:10.1021/jo00166a003. ISSN 0022-3263.
  8. [8]
    "3-Nitrooxetane | C3H5NO3 | ChemSpider". www.chemspider.com. Retrieved 2022-12-28.
  9. [9]
    Willenbring, Dan; Tantillo, Dean J. (April 2008). "Mechanistic possibilities for oxetane formation in the biosynthesis of Taxol's D ring". Russian Journal of General Chemistry. 78 (4): 723–731. doi:10.1134/S1070363208040336. S2CID 98056619.
  10. [10]
    Hans Jürgen Bestmann; Otto Vostrowsky; Werner Stransky (1976). Pheromone, X. Eine stereoselektive Synthese des (Z)-7,8-Epoxy-2-methyloctadecans (Disparlure). , 109(10), 3375–3378. doi:10.1002/cber.19761091015
  11. [11]
    Patai 1967, p. 425.
  12. [12]
    Patai 1967, pp. 63, 425.
  13. [13]
    Patai 1967, pp. 67–68.
  14. [14]
    Patai 1967, pp. 376–377.
  15. [15]
    Patai, Saul, ed. (1967). The Chemistry of the Ether Linkage. The Chemistry of Functional Groups. London: Interscience / William Clowes and Sons. pp. 28–30. LCCN 66-30401.
  16. [16]
    Patai 1967, p. 696.
  17. [17]
    Patai 1967, pp. 697, 700.
  18. [18]
    Penczek & Penczek (1963), "Kinetics and mechanism of heterogeneous polymerization of 3,3-bis(chloromethyl)oxetane catalyzed by gaseous BF3" in Die Makromolekuläre Chemie. Wiley.
  19. [19]
    Patai 1967, p. 380.
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